EP0175384A2 - Ceramic materials with increased crystallinity from silazane polymers - Google Patents
Ceramic materials with increased crystallinity from silazane polymers Download PDFInfo
- Publication number
- EP0175384A2 EP0175384A2 EP85111950A EP85111950A EP0175384A2 EP 0175384 A2 EP0175384 A2 EP 0175384A2 EP 85111950 A EP85111950 A EP 85111950A EP 85111950 A EP85111950 A EP 85111950A EP 0175384 A2 EP0175384 A2 EP 0175384A2
- Authority
- EP
- European Patent Office
- Prior art keywords
- iron
- compounds
- sinh
- copper
- silazane polymer
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 81
- 229910010293 ceramic material Inorganic materials 0.000 title claims abstract description 49
- 230000001965 increasing effect Effects 0.000 title claims abstract description 32
- 238000000034 method Methods 0.000 claims abstract description 42
- 229910010272 inorganic material Inorganic materials 0.000 claims abstract description 41
- 150000002484 inorganic compounds Chemical class 0.000 claims abstract description 40
- 239000012298 atmosphere Substances 0.000 claims abstract description 16
- 150000002506 iron compounds Chemical class 0.000 claims abstract description 11
- 150000001869 cobalt compounds Chemical class 0.000 claims abstract description 10
- 150000002816 nickel compounds Chemical class 0.000 claims abstract description 10
- 239000005749 Copper compound Substances 0.000 claims abstract description 9
- 150000001880 copper compounds Chemical class 0.000 claims abstract description 9
- 239000000919 ceramic Substances 0.000 claims description 15
- 238000002156 mixing Methods 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000000463 material Substances 0.000 claims description 5
- 239000000203 mixture Substances 0.000 abstract description 32
- 238000010304 firing Methods 0.000 abstract description 15
- 229910052581 Si3N4 Inorganic materials 0.000 abstract description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 21
- 239000000654 additive Substances 0.000 description 21
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- 229910010271 silicon carbide Inorganic materials 0.000 description 17
- 238000002441 X-ray diffraction Methods 0.000 description 16
- -1 iron (III) octoate Chemical compound 0.000 description 15
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 14
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 13
- 239000000243 solution Substances 0.000 description 12
- 239000000460 chlorine Substances 0.000 description 11
- 229910052734 helium Inorganic materials 0.000 description 11
- 239000001307 helium Substances 0.000 description 11
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 229910052742 iron Inorganic materials 0.000 description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 10
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 229910052801 chlorine Inorganic materials 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 239000000835 fiber Substances 0.000 description 8
- 238000001238 wet grinding Methods 0.000 description 8
- 125000004432 carbon atom Chemical group C* 0.000 description 7
- 238000000197 pyrolysis Methods 0.000 description 7
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical class [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- VNZQQAVATKSIBR-UHFFFAOYSA-L copper;octanoate Chemical compound [Cu+2].CCCCCCCC([O-])=O.CCCCCCCC([O-])=O VNZQQAVATKSIBR-UHFFFAOYSA-L 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 125000000217 alkyl group Chemical group 0.000 description 4
- 230000002708 enhancing effect Effects 0.000 description 4
- 239000000945 filler Substances 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 4
- 238000003801 milling Methods 0.000 description 4
- 150000001367 organochlorosilanes Chemical class 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 3
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical class [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical class [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 3
- 238000009837 dry grinding Methods 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 3
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 150000004756 silanes Chemical class 0.000 description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 239000005046 Chlorosilane Substances 0.000 description 2
- VMQMZMRVKUZKQL-UHFFFAOYSA-N Cu+ Chemical class [Cu+] VMQMZMRVKUZKQL-UHFFFAOYSA-N 0.000 description 2
- QXNVGIXVLWOKEQ-UHFFFAOYSA-N Disodium Chemical compound [Na][Na] QXNVGIXVLWOKEQ-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- BQZYCERHRYZTOT-UHFFFAOYSA-N [O-2].[O-2].[O-2].O.[Fe+2].[Fe+2].[Cu+2] Chemical compound [O-2].[O-2].[O-2].O.[Fe+2].[Fe+2].[Cu+2] BQZYCERHRYZTOT-UHFFFAOYSA-N 0.000 description 2
- 239000002671 adjuvant Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical class Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- IJOOHPMOJXWVHK-UHFFFAOYSA-N chlorotrimethylsilane Chemical compound C[Si](C)(C)Cl IJOOHPMOJXWVHK-UHFFFAOYSA-N 0.000 description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 2
- JAWGVVJVYSANRY-UHFFFAOYSA-N cobalt(3+) Chemical class [Co+3] JAWGVVJVYSANRY-UHFFFAOYSA-N 0.000 description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L copper(II) hydroxide Inorganic materials [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(i) oxide Chemical compound [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 2
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 description 2
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 description 2
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 description 2
- FFUAGWLWBBFQJT-UHFFFAOYSA-N hexamethyldisilazane Chemical compound C[Si](C)(C)N[Si](C)(C)C FFUAGWLWBBFQJT-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 description 2
- JEALIFOJMITGDQ-UHFFFAOYSA-N iron(3+);nickel(2+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Ni+2].[Ni+2] JEALIFOJMITGDQ-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 2
- JLUFWMXJHAVVNN-UHFFFAOYSA-N methyltrichlorosilane Chemical compound C[Si](Cl)(Cl)Cl JLUFWMXJHAVVNN-UHFFFAOYSA-N 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 235000010755 mineral Nutrition 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- GNMQOUGYKPVJRR-UHFFFAOYSA-N nickel(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ni+3].[Ni+3] GNMQOUGYKPVJRR-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 229920002959 polymer blend Polymers 0.000 description 2
- 239000000523 sample Substances 0.000 description 2
- 235000015096 spirit Nutrition 0.000 description 2
- AWDBHOZBRXWRKS-UHFFFAOYSA-N tetrapotassium;iron(6+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+6].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] AWDBHOZBRXWRKS-UHFFFAOYSA-N 0.000 description 2
- WFUDBPZFGCNRDM-UHFFFAOYSA-N 1-butylcyclopenta-1,3-diene;cyclopenta-1,3-diene;iron(2+) Chemical compound [Fe+2].C=1C=C[CH-]C=1.CCCCC1=CC=C[CH-]1 WFUDBPZFGCNRDM-UHFFFAOYSA-N 0.000 description 1
- GPWNWKWQOLEVEQ-UHFFFAOYSA-N 2,4-diaminopyrimidine-5-carbaldehyde Chemical compound NC1=NC=C(C=O)C(N)=N1 GPWNWKWQOLEVEQ-UHFFFAOYSA-N 0.000 description 1
- TXRXQYAWKZOYLW-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;copper Chemical compound [Cu].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O TXRXQYAWKZOYLW-UHFFFAOYSA-N 0.000 description 1
- QUKLPQSKLABKQO-UHFFFAOYSA-N 2-azanidylethylazanide;cobalt Chemical compound [Co].[NH-]CC[NH-].[NH-]CC[NH-].[NH-]CC[NH-] QUKLPQSKLABKQO-UHFFFAOYSA-N 0.000 description 1
- ULUYRVWYCIOFRV-UHFFFAOYSA-K 2-ethylhexanoate;iron(3+) Chemical compound [Fe+3].CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O.CCCCC(CC)C([O-])=O ULUYRVWYCIOFRV-UHFFFAOYSA-K 0.000 description 1
- RURZQVYCZPJWMN-UHFFFAOYSA-N 2-ethylhexanoic acid;nickel Chemical compound [Ni].CCCCC(CC)C(O)=O.CCCCC(CC)C(O)=O RURZQVYCZPJWMN-UHFFFAOYSA-N 0.000 description 1
- LSLSVVJPMABPLC-UHFFFAOYSA-L 4-cyclohexylbutanoate;nickel(2+) Chemical compound [Ni+2].[O-]C(=O)CCCC1CCCCC1.[O-]C(=O)CCCC1CCCCC1 LSLSVVJPMABPLC-UHFFFAOYSA-L 0.000 description 1
- BSYNRYMUTXBXSQ-FOQJRBATSA-N 59096-14-9 Chemical compound CC(=O)OC1=CC=CC=C1[14C](O)=O BSYNRYMUTXBXSQ-FOQJRBATSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910021580 Cobalt(II) chloride Inorganic materials 0.000 description 1
- 229910021582 Cobalt(II) fluoride Inorganic materials 0.000 description 1
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 description 1
- 229910021584 Cobalt(II) iodide Inorganic materials 0.000 description 1
- 229910021581 Cobalt(III) chloride Inorganic materials 0.000 description 1
- OCUCCJIRFHNWBP-IYEMJOQQSA-L Copper gluconate Chemical compound [Cu+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O OCUCCJIRFHNWBP-IYEMJOQQSA-L 0.000 description 1
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 1
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 1
- 229910021590 Copper(II) bromide Inorganic materials 0.000 description 1
- 229910021592 Copper(II) chloride Inorganic materials 0.000 description 1
- 229910021594 Copper(II) fluoride Inorganic materials 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical class [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical class [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910021575 Iron(II) bromide Inorganic materials 0.000 description 1
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 1
- 229910021579 Iron(II) iodide Inorganic materials 0.000 description 1
- 229910021576 Iron(III) bromide Inorganic materials 0.000 description 1
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 1
- 229910021585 Nickel(II) bromide Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 229910021587 Nickel(II) fluoride Inorganic materials 0.000 description 1
- 229910021588 Nickel(II) iodide Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical class [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- DLKQCLIBMWAKOH-UHFFFAOYSA-N [Co+4] Chemical class [Co+4] DLKQCLIBMWAKOH-UHFFFAOYSA-N 0.000 description 1
- XUKVMZJGMBEQDE-UHFFFAOYSA-N [Co](=S)=S Chemical compound [Co](=S)=S XUKVMZJGMBEQDE-UHFFFAOYSA-N 0.000 description 1
- RHQKKJPJCHGKQO-UHFFFAOYSA-N [Cu+2].[O-][Cr]([O-])=O Chemical compound [Cu+2].[O-][Cr]([O-])=O RHQKKJPJCHGKQO-UHFFFAOYSA-N 0.000 description 1
- CGJXKMLRGZEZDO-UHFFFAOYSA-N [Cu+]=S Chemical compound [Cu+]=S CGJXKMLRGZEZDO-UHFFFAOYSA-N 0.000 description 1
- DOUYOVFHQKVSSJ-UHFFFAOYSA-N [Fe].c1cccc1.CC(C)(C)c1cccc1 Chemical compound [Fe].c1cccc1.CC(C)(C)c1cccc1 DOUYOVFHQKVSSJ-UHFFFAOYSA-N 0.000 description 1
- ZQQGQJKVMMDIKF-UHFFFAOYSA-N [Ni+4] Chemical class [Ni+4] ZQQGQJKVMMDIKF-UHFFFAOYSA-N 0.000 description 1
- HNDMNBUITRNJKK-UHFFFAOYSA-N [Ni](=S)=S Chemical compound [Ni](=S)=S HNDMNBUITRNJKK-UHFFFAOYSA-N 0.000 description 1
- 229910017878 a-Si3N4 Inorganic materials 0.000 description 1
- 229910021431 alpha silicon carbide Inorganic materials 0.000 description 1
- XGGLLRJQCZROSE-UHFFFAOYSA-K ammonium iron(iii) sulfate Chemical compound [NH4+].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O XGGLLRJQCZROSE-UHFFFAOYSA-K 0.000 description 1
- DAPUDVOJPZKTSI-UHFFFAOYSA-L ammonium nickel sulfate Chemical compound [NH4+].[NH4+].[Ni+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DAPUDVOJPZKTSI-UHFFFAOYSA-L 0.000 description 1
- DOIHHHHNLGDDRE-UHFFFAOYSA-N azanide;copper;copper(1+) Chemical compound [NH2-].[Cu].[Cu].[Cu+] DOIHHHHNLGDDRE-UHFFFAOYSA-N 0.000 description 1
- RWCCWEUUXYIKHB-UHFFFAOYSA-N benzophenone Chemical compound C=1C=CC=CC=1C(=O)C1=CC=CC=C1 RWCCWEUUXYIKHB-UHFFFAOYSA-N 0.000 description 1
- QDWJUBJKEHXSMT-UHFFFAOYSA-N boranylidynenickel Chemical compound [Ni]#B QDWJUBJKEHXSMT-UHFFFAOYSA-N 0.000 description 1
- NBFCJULAAWWTBL-UHFFFAOYSA-N buta-1,3-diene;carbon monoxide;iron Chemical compound [Fe].[O+]#[C-].[O+]#[C-].[O+]#[C-].C=CC=C NBFCJULAAWWTBL-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- CVCSGXJPONFHRC-UHFFFAOYSA-N carbon monoxide;cobalt;nitroxyl anion Chemical compound [Co].[O+]#[C-].[O+]#[C-].[O+]#[C-].O=[N-] CVCSGXJPONFHRC-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229910001567 cementite Inorganic materials 0.000 description 1
- NEHMKBQYUWJMIP-NJFSPNSNSA-N chloro(114C)methane Chemical compound [14CH3]Cl NEHMKBQYUWJMIP-NJFSPNSNSA-N 0.000 description 1
- KQHIGRPLCKIXNJ-UHFFFAOYSA-N chloro-methyl-silylsilane Chemical class C[SiH]([SiH3])Cl KQHIGRPLCKIXNJ-UHFFFAOYSA-N 0.000 description 1
- NSYALVBBDKTCLE-UHFFFAOYSA-K chloropentamminecobalt chloride Chemical compound N.N.N.N.N.[Cl-].[Cl-].[Cl-].[Co+3] NSYALVBBDKTCLE-UHFFFAOYSA-K 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical class [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 1
- NPAQSKHBTMUERN-UHFFFAOYSA-L cobalt(2+);2-[2-[(2-oxidophenyl)methylideneamino]ethyliminomethyl]phenolate Chemical compound [Co+2].[O-]C1=CC=CC=C1C=NCCN=CC1=CC=CC=C1[O-] NPAQSKHBTMUERN-UHFFFAOYSA-L 0.000 description 1
- YBXHPSXGXLGNBR-UHFFFAOYSA-L cobalt(2+);4-cyclohexylbutanoate Chemical compound [Co+2].[O-]C(=O)CCCC1CCCCC1.[O-]C(=O)CCCC1CCCCC1 YBXHPSXGXLGNBR-UHFFFAOYSA-L 0.000 description 1
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 0.000 description 1
- GAYAMOAYBXKUII-UHFFFAOYSA-L cobalt(2+);dibenzoate Chemical compound [Co+2].[O-]C(=O)C1=CC=CC=C1.[O-]C(=O)C1=CC=CC=C1 GAYAMOAYBXKUII-UHFFFAOYSA-L 0.000 description 1
- FJNQKAYLLNDYTJ-UHFFFAOYSA-N cobalt(2+);diborate Chemical compound [Co+2].[Co+2].[Co+2].[O-]B([O-])[O-].[O-]B([O-])[O-] FJNQKAYLLNDYTJ-UHFFFAOYSA-N 0.000 description 1
- AVWLPUQJODERGA-UHFFFAOYSA-L cobalt(2+);diiodide Chemical compound [Co+2].[I-].[I-] AVWLPUQJODERGA-UHFFFAOYSA-L 0.000 description 1
- BSUSEPIPTZNHMN-UHFFFAOYSA-L cobalt(2+);diperchlorate Chemical compound [Co+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O BSUSEPIPTZNHMN-UHFFFAOYSA-L 0.000 description 1
- INDBQWVYFLTCFF-UHFFFAOYSA-L cobalt(2+);dithiocyanate Chemical compound [Co+2].[S-]C#N.[S-]C#N INDBQWVYFLTCFF-UHFFFAOYSA-L 0.000 description 1
- LZPCVCSHOIEYNF-UHFFFAOYSA-L cobalt(2+);ethane-1,2-diamine;sulfate Chemical compound [Co+2].NCCN.NCCN.NCCN.[O-]S([O-])(=O)=O LZPCVCSHOIEYNF-UHFFFAOYSA-L 0.000 description 1
- XNGOCNMGDFPQTP-UHFFFAOYSA-N cobalt(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Fe+3].[Fe+3].[Co+2].[Co+2] XNGOCNMGDFPQTP-UHFFFAOYSA-N 0.000 description 1
- MULYSYXKGICWJF-UHFFFAOYSA-L cobalt(2+);oxalate Chemical compound [Co+2].[O-]C(=O)C([O-])=O MULYSYXKGICWJF-UHFFFAOYSA-L 0.000 description 1
- IUYLTEAJCNAMJK-UHFFFAOYSA-N cobalt(2+);oxygen(2-) Chemical compound [O-2].[Co+2] IUYLTEAJCNAMJK-UHFFFAOYSA-N 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- 229910000001 cobalt(II) carbonate Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(II) oxide Inorganic materials [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 229910000335 cobalt(II) sulfate Inorganic materials 0.000 description 1
- BZRRQSJJPUGBAA-UHFFFAOYSA-L cobalt(ii) bromide Chemical compound Br[Co]Br BZRRQSJJPUGBAA-UHFFFAOYSA-L 0.000 description 1
- YCYBZKSMUPTWEE-UHFFFAOYSA-L cobalt(ii) fluoride Chemical compound F[Co]F YCYBZKSMUPTWEE-UHFFFAOYSA-L 0.000 description 1
- FCEOGYWNOSBEPV-FDGPNNRMSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FCEOGYWNOSBEPV-FDGPNNRMSA-N 0.000 description 1
- PKSIZOUDEUREFF-UHFFFAOYSA-N cobalt;dihydrate Chemical compound O.O.[Co] PKSIZOUDEUREFF-UHFFFAOYSA-N 0.000 description 1
- RKBAPHPQTADBIK-UHFFFAOYSA-N cobalt;hexacyanide Chemical compound [Co].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] RKBAPHPQTADBIK-UHFFFAOYSA-N 0.000 description 1
- JUPWRUDTZGBNEX-UHFFFAOYSA-N cobalt;pentane-2,4-dione Chemical compound [Co].CC(=O)CC(C)=O.CC(=O)CC(C)=O.CC(=O)CC(C)=O JUPWRUDTZGBNEX-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 239000013068 control sample Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- CERUGEBHQUKZJV-UHFFFAOYSA-L copper ethane-1,2-diamine sulfate Chemical compound [Cu++].NCCN.NCCN.NCCN.[O-]S([O-])(=O)=O CERUGEBHQUKZJV-UHFFFAOYSA-L 0.000 description 1
- WILFNLHOTDCRAO-UHFFFAOYSA-N copper(1+);2-methylpropan-2-olate Chemical compound [Cu+].CC(C)(C)[O-] WILFNLHOTDCRAO-UHFFFAOYSA-N 0.000 description 1
- RFKZUAOAYVHBOY-UHFFFAOYSA-M copper(1+);acetate Chemical compound [Cu+].CC([O-])=O RFKZUAOAYVHBOY-UHFFFAOYSA-M 0.000 description 1
- JJNATTOAHGMEHT-UHFFFAOYSA-M copper(1+);iodate Chemical compound [Cu+].[O-]I(=O)=O JJNATTOAHGMEHT-UHFFFAOYSA-M 0.000 description 1
- PDZKZMQQDCHTNF-UHFFFAOYSA-M copper(1+);thiocyanate Chemical compound [Cu+].[S-]C#N PDZKZMQQDCHTNF-UHFFFAOYSA-M 0.000 description 1
- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 1
- 229910001497 copper(II) tetrafluoroborate Inorganic materials 0.000 description 1
- NKNDPYCGAZPOFS-UHFFFAOYSA-M copper(i) bromide Chemical compound Br[Cu] NKNDPYCGAZPOFS-UHFFFAOYSA-M 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 1
- GWFAVIIMQDUCRA-UHFFFAOYSA-L copper(ii) fluoride Chemical compound [F-].[F-].[Cu+2] GWFAVIIMQDUCRA-UHFFFAOYSA-L 0.000 description 1
- YRNNKGFMTBWUGL-UHFFFAOYSA-L copper(ii) perchlorate Chemical compound [Cu+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O YRNNKGFMTBWUGL-UHFFFAOYSA-L 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- ZGMZTUJLZVTXNR-UHFFFAOYSA-N copper;4-cyclohexylbutanoic acid Chemical compound [Cu].OC(=O)CCCC1CCCCC1.OC(=O)CCCC1CCCCC1 ZGMZTUJLZVTXNR-UHFFFAOYSA-N 0.000 description 1
- VUWZDHZJZQTKAY-UHFFFAOYSA-L copper;benzenethiolate Chemical compound [Cu+2].[S-]C1=CC=CC=C1.[S-]C1=CC=CC=C1 VUWZDHZJZQTKAY-UHFFFAOYSA-L 0.000 description 1
- AEJIMXVJZFYIHN-UHFFFAOYSA-N copper;dihydrate Chemical compound O.O.[Cu] AEJIMXVJZFYIHN-UHFFFAOYSA-N 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000011642 cupric gluconate Substances 0.000 description 1
- 235000019856 cupric gluconate Nutrition 0.000 description 1
- GPRSOIDYHMXAGW-UHFFFAOYSA-N cyclopenta-1,3-diene cyclopentanecarboxylic acid iron Chemical compound [CH-]1[CH-][CH-][C-]([CH-]1)C(=O)O.[CH-]1C=CC=C1.[Fe] GPRSOIDYHMXAGW-UHFFFAOYSA-N 0.000 description 1
- KZPXREABEBSAQM-UHFFFAOYSA-N cyclopenta-1,3-diene;nickel(2+) Chemical compound [Ni+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KZPXREABEBSAQM-UHFFFAOYSA-N 0.000 description 1
- JJJSTEANRWLZBH-UHFFFAOYSA-N cyclopentane;1-cyclopentyl-n,n-dimethylmethanamine;iron Chemical compound [Fe].[CH]1[CH][CH][CH][CH]1.CN(C)C[C]1[CH][CH][CH][CH]1 JJJSTEANRWLZBH-UHFFFAOYSA-N 0.000 description 1
- 125000004989 dicarbonyl group Chemical group 0.000 description 1
- RZHIALGQQJESEK-UHFFFAOYSA-L dichloronickel;triethylphosphane Chemical compound Cl[Ni]Cl.CCP(CC)CC.CCP(CC)CC RZHIALGQQJESEK-UHFFFAOYSA-L 0.000 description 1
- BUMGIEFFCMBQDG-UHFFFAOYSA-N dichlorosilicon Chemical compound Cl[Si]Cl BUMGIEFFCMBQDG-UHFFFAOYSA-N 0.000 description 1
- ZMMDPCMYTCRWFF-UHFFFAOYSA-J dicopper;carbonate;dihydroxide Chemical compound [OH-].[OH-].[Cu+2].[Cu+2].[O-]C([O-])=O ZMMDPCMYTCRWFF-UHFFFAOYSA-J 0.000 description 1
- PZPGRFITIJYNEJ-UHFFFAOYSA-N disilane Chemical compound [SiH3][SiH3] PZPGRFITIJYNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- XTFBVEJGQBZKHL-UHFFFAOYSA-L ethane-1,2-diamine nickel(2+) sulfate Chemical compound [Ni+2].NCCN.NCCN.NCCN.[O-]S([O-])(=O)=O XTFBVEJGQBZKHL-UHFFFAOYSA-L 0.000 description 1
- KLLMHEWAYVXMSW-UHFFFAOYSA-L ethane-1,2-diamine;iron(2+);sulfuric acid;sulfate Chemical compound [Fe+2].NCCN.OS([O-])(=O)=O.OS([O-])(=O)=O KLLMHEWAYVXMSW-UHFFFAOYSA-L 0.000 description 1
- UEUDBBQFZIMOQJ-UHFFFAOYSA-K ferric ammonium oxalate Chemical compound [NH4+].[NH4+].[NH4+].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O UEUDBBQFZIMOQJ-UHFFFAOYSA-K 0.000 description 1
- VEPSWGHMGZQCIN-UHFFFAOYSA-H ferric oxalate Chemical compound [Fe+3].[Fe+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O VEPSWGHMGZQCIN-UHFFFAOYSA-H 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 239000004222 ferrous gluconate Substances 0.000 description 1
- 235000013924 ferrous gluconate Nutrition 0.000 description 1
- ALDOUWLIYKWJTN-UHFFFAOYSA-N fluoro(dioxido)borane;nickel(2+) Chemical compound [Ni+2].[O-]B([O-])F ALDOUWLIYKWJTN-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 238000010952 in-situ formation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 1
- 229910001337 iron nitride Inorganic materials 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- CKFMJXZQTNRXGX-UHFFFAOYSA-L iron(2+);diperchlorate Chemical compound [Fe+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O CKFMJXZQTNRXGX-UHFFFAOYSA-L 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- WBJZTOZJJYAKHQ-UHFFFAOYSA-K iron(3+) phosphate Chemical compound [Fe+3].[O-]P([O-])([O-])=O WBJZTOZJJYAKHQ-UHFFFAOYSA-K 0.000 description 1
- AQBLLJNPHDIAPN-LNTINUHCSA-K iron(3+);(z)-4-oxopent-2-en-2-olate Chemical compound [Fe+3].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O AQBLLJNPHDIAPN-LNTINUHCSA-K 0.000 description 1
- BLZYFIGKQXJJQM-UHFFFAOYSA-L iron(3+);acetate;hydroxide Chemical compound [OH-].[Fe+3].CC([O-])=O BLZYFIGKQXJJQM-UHFFFAOYSA-L 0.000 description 1
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 1
- 229910000155 iron(II) phosphate Inorganic materials 0.000 description 1
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 1
- 229910000399 iron(III) phosphate Inorganic materials 0.000 description 1
- LNOZJRCUHSPCDZ-UHFFFAOYSA-L iron(ii) acetate Chemical compound [Fe+2].CC([O-])=O.CC([O-])=O LNOZJRCUHSPCDZ-UHFFFAOYSA-L 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- FZGIHSNZYGFUGM-UHFFFAOYSA-L iron(ii) fluoride Chemical compound [F-].[F-].[Fe+2] FZGIHSNZYGFUGM-UHFFFAOYSA-L 0.000 description 1
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 description 1
- BQZGVMWPHXIKEQ-UHFFFAOYSA-L iron(ii) iodide Chemical compound [Fe+2].[I-].[I-] BQZGVMWPHXIKEQ-UHFFFAOYSA-L 0.000 description 1
- SDEKDNPYZOERBP-UHFFFAOYSA-H iron(ii) phosphate Chemical compound [Fe+2].[Fe+2].[Fe+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O SDEKDNPYZOERBP-UHFFFAOYSA-H 0.000 description 1
- SHXXPRJOPFJRHA-UHFFFAOYSA-K iron(iii) fluoride Chemical compound F[Fe](F)F SHXXPRJOPFJRHA-UHFFFAOYSA-K 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910003465 moissanite Inorganic materials 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- FBMUYWXYWIZLNE-UHFFFAOYSA-N nickel phosphide Chemical compound [Ni]=P#[Ni] FBMUYWXYWIZLNE-UHFFFAOYSA-N 0.000 description 1
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 1
- IPLJNQFXJUCRNH-UHFFFAOYSA-L nickel(2+);dibromide Chemical compound [Ni+2].[Br-].[Br-] IPLJNQFXJUCRNH-UHFFFAOYSA-L 0.000 description 1
- ZLQBNKOPBDZKDP-UHFFFAOYSA-L nickel(2+);diperchlorate Chemical compound [Ni+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O ZLQBNKOPBDZKDP-UHFFFAOYSA-L 0.000 description 1
- DOLZKNFSRCEOFV-UHFFFAOYSA-L nickel(2+);oxalate Chemical compound [Ni+2].[O-]C(=O)C([O-])=O DOLZKNFSRCEOFV-UHFFFAOYSA-L 0.000 description 1
- JDRCAGKFDGHRNQ-UHFFFAOYSA-N nickel(3+) Chemical class [Ni+3] JDRCAGKFDGHRNQ-UHFFFAOYSA-N 0.000 description 1
- 229910000008 nickel(II) carbonate Inorganic materials 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 1
- AIYYMMQIMJOTBM-UHFFFAOYSA-L nickel(ii) acetate Chemical compound [Ni+2].CC([O-])=O.CC([O-])=O AIYYMMQIMJOTBM-UHFFFAOYSA-L 0.000 description 1
- ZULUUIKRFGGGTL-UHFFFAOYSA-L nickel(ii) carbonate Chemical compound [Ni+2].[O-]C([O-])=O ZULUUIKRFGGGTL-UHFFFAOYSA-L 0.000 description 1
- DBJLJFTWODWSOF-UHFFFAOYSA-L nickel(ii) fluoride Chemical compound F[Ni]F DBJLJFTWODWSOF-UHFFFAOYSA-L 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 1
- BFSQJYRFLQUZKX-UHFFFAOYSA-L nickel(ii) iodide Chemical compound I[Ni]I BFSQJYRFLQUZKX-UHFFFAOYSA-L 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 150000002902 organometallic compounds Chemical class 0.000 description 1
- 150000003961 organosilicon compounds Chemical class 0.000 description 1
- 229920000307 polymer substrate Polymers 0.000 description 1
- 229920001709 polysilazane Polymers 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- VSRUWRBJHJVUDC-UHFFFAOYSA-L potassium;2-hydroxy-2-oxoacetate;iron(3+);oxalic acid Chemical compound [K+].[Fe+3].OC(=O)C(O)=O.OC(=O)C([O-])=O.OC(=O)C([O-])=O VSRUWRBJHJVUDC-UHFFFAOYSA-L 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- ZXQVPEBHZMCRMC-UHFFFAOYSA-R tetraazanium;iron(2+);hexacyanide Chemical compound [NH4+].[NH4+].[NH4+].[NH4+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] ZXQVPEBHZMCRMC-UHFFFAOYSA-R 0.000 description 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 description 1
- IEKWPPTXWFKANS-UHFFFAOYSA-K trichlorocobalt Chemical compound Cl[Co](Cl)Cl IEKWPPTXWFKANS-UHFFFAOYSA-K 0.000 description 1
- ZEBNDJQGEZXBCR-UHFFFAOYSA-H trisodium;cobalt(3+);hexanitrite Chemical compound [Na+].[Na+].[Na+].[Co+3].[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O.[O-]N=O ZEBNDJQGEZXBCR-UHFFFAOYSA-H 0.000 description 1
- NXXJJPQQCLIRPD-UHFFFAOYSA-H trisodium;hexafluoroiron(3-) Chemical compound [F-].[F-].[F-].[F-].[F-].[F-].[Na+].[Na+].[Na+].[Fe+3] NXXJJPQQCLIRPD-UHFFFAOYSA-H 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/009—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone characterised by the material treated
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/56—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides
- C04B35/565—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide
- C04B35/571—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on carbides or oxycarbides based on silicon carbide obtained from Si-containing polymer precursors or organosilicon monomers
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/515—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics
- C04B35/58—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides
- C04B35/584—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride
- C04B35/589—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on non-oxide ceramics based on borides, nitrides, i.e. nitrides, oxynitrides, carbonitrides or oxycarbonitrides or silicides based on silicon nitride obtained from Si-containing polymer precursors or organosilicon monomers
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- C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
- C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
- C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
- C04B41/5053—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials non-oxide ceramics
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/10—Metal compounds
- C08K3/105—Compounds containing metals of Groups 1 to 3 or of Groups 11 to 13 of the Periodic Table
Definitions
- This invention relates to the preparation of ceramic materials with increased crystallinity. More specifically, this invention relates to the preparation of ceramic materials with increased levels of crystalline SiC and/or Si 3 N 4 .
- the ceramic materials of this invention are obtained by firing a mixture of a R 3 SiNH-containing silazane polymer and certain inorganic compounds to an elevated temperature in an inert atmosphere or in a vacuum.
- the additives that allow for ceramic materials with increased crystallinity include iron compounds, cobalt compounds, nickel compounds, and copper compounds.
- Ceramic material prepared from R 3 SirlH-containing silazane polymers are known to the art. Gaul, in U.S. Patent No. 4,340,619 (issued July 20, 1982), prepared ceramic materials by firing at elevated temperatures in an inert atmosphere a R 3 SiNH-containing silazane polymer prepared by contacting and reacting, in an inert, essentially anhydrous atmosphere, chlorine-containing disilanes with disilazanes.
- the ceramic material of U.S. Patent No. 4,340,619 contained crystalline SiC and/or Si 3 N 4 only when the R 3 SiNH-containing silazane polymer was fired to at least 1600°C.
- This invention relates to a method of preparing a ceramic material with increased crystallinity, said method comprising heating a modified R 3 SiNH-containing silizane polymer in an inert atmosphere or in a vacuum to a temperature of at least 750°C until said modified R 3 SiNH-containing silazane polymer is converted to a ceramic material with increased crystallinity relative to a non-modified R 3 SiNH-containing silazane polymer heated under the same conditions, wherein said modified R 3 SiNH-containing silazane polymer is prepared by mixing the non-modified R 3 SiNH-containing silazane polymer with an effective, crystallinity increasing, amount of an inorganic compound selected from the group consisting of iron compounds, cobalt compounds, nickel compounds, and copper compounds.
- the process of this invention is carried out by first mixing a R 3 SiNH-containing silazane polymer with an effective amount of an inorganic compound and then firing the resulting mixture to an elevated temperature under an inert atmosphere or in a vacuum until the resulting mixture is converted to a ceramic material.
- Suitable inorganic additives for the practice of the invention include iron compounds, cobalt compounds, nickel compounds, and copper compounds. These inorganic compounds include organometallic compounds as detailed below.
- Suitable iron compounds include iron (II) compounds, iron (III) compounds and zero valence iron compounds.
- suitable iron compounds include iron (II) bromide, iron (III) bromide, iron (II) ethylenedi- ammonium sulfate, iron (II) oxalate, iron (III) octoate, iron (II) acetate, iron (III) acetate hydroxide, disodium tetracarbonylferrate, sodium pentacyanonitrosylferrate (III), pentacarbonyliron, ammonium trioxalatoferrate (III), ammonium hexacyanoferrate (II), potassium hexacyanoferrate (III), potassium trioxalatoferrate (III), potassium hexacyanoferrate (II), dicarbonylcyclopentadienyliodoiron, butadienetricarbonyliron, bis(cyclopentadienyl)iron, iron (II)
- Suitable cobalt compounds include cobalt (II) compounds, cobalt (III) compounds, cobalt (IV) compounds, and zero valence cobalt compounds.
- suitable cobalt compounds include cobalt (II) tetrafluoroborate, cobalt (II) borate, cobalt (II) bromide, cobalt (II) carbonate, cobalt (II) thiocyanate, cobalt (II) oxalate, tricarbonylnitrosyl cobalt, cobalt (II) acetate, tris(ethylenediamine) cobalt (III) chloride, tris(ethylenediamine) cobalt (II) sulfate, potassium hexacyanocobaltate (III), cobalt (II) octoate, dicarbonylcyclopentadienyl cobalt, bis(cyclopentadienyl) cobalt, cobalt (II) acetylacet
- Suitable nickel compounds include nickel (II) compounds, nickel (III) compounds, nickel (IV) compounds, and zero valence nickel compounds.
- suitable nickel compounds include nickel boride, nickel tetrafluoroborate, nickel (II) bromide, nickel (II) carbonate, nickel (II) oxalate, nickel (II) acetate, tetracarbonyl nickel, tri(ethylenediamine) nickel (II) sulfate, bis(cyclopentadienyl) nickel, nickel (II) acetoacetonate, bis(triethylphosphine) nickel (II) chloride, nickel (II) n-phenyl- glycinate, nickel (II) 2-ethylhexanoate, nickel cyclohexanebutyrate, nickel (II) chloride, nickel (II) perchlorate, nickel (II) fluoride, potassium hexafluoronickelate (IV), nickel hexa
- Suitable copper compounds include copper (I) compounds and copper (II) compounds.
- suitable copper compounds include copper (II) tetrafluoroborate, copper (I) bromide, copper (II) bromide, copper (I) cyanide, copper (I) thiocyanate, copper (I) acetate, copper (II) acetate, copper (II) octoate, copper (I) t-butoxide, copper thiophenoxide, tri(ethylenediamine) copper (II) sulfate, disodium salt of ethylenediamine-tetraacetic acid copper (II), copper (II) acetylacetonate, copper (II) octoate, copper (II) gluconate, copper salt of acetylsalicylic acid, copper (II) cyclohexanebutyrate, copper '(I) chloride, copper (II) chloride, copper (II) perchlorate, copper (
- the method of mixing the R 3 SiNH-containing silazane polymer and the inorganic compound is not critical. It is preferred that the R 3 SiNH-containing silazane polymer and the inorganic compound be well mixed in order to obtain ceramic materials or articles where the amount of crystalline Si 3 N 4 and/or SiC does not vary appreciably throughout the ceramic material or article. Using an organic solvent such a toluene helps to insure that the two components are well mixed. When a solvent is employed to mix the R 3 SiNH-containing.silazane polymer and the inorganic material, the solvent should be removed by conventional means prior to heating the mixture to an elevated temperature in order form a ceramic material.
- the R 3 SiNH-containing silazane polymer and the inorganic compounds may also be mixed on 3 roll mills by simply adding the ingredients and making several passes on the mill. As will be apparent to one of ordinary skill in the art, other mixing techniques may be used that will result in ceramic materials or articles with the level of crystallinity uniform throughout the ceramic material or article.
- the R 3 SiNH-containing silazane polymer is mixed with an effective amount of an inorganic compound.
- an effective amount of the inorganic compound we mean that amount which results in increased crystallinity in the resulting ceramic material.
- the inorganic compound is added at such a level so as to obtain a mixture containing the R 3 SiNH-containing silazane polymer and about 0.1 to 2.0 weight percent of the metal associated with the inorganic compound.
- the inorganic compound may be added at higher levels although no added benefits are noted.
- the increase in crystallinity of the ceramic material of this invention is measured by comparison with the crystallinity of a ceramic material obtained by firing the same R 3 SiNH-containing silazane polymer, without any added inorganic compounds, under the same experimental conditions.
- the mixture of R 3 SiNH-containing silazane polymer and an effective amount of an inorganic compound is fired to elevated temperatures of at least 750°C under an inert atmosphere or in a vacuum until the mixture is converted to a ceramic material.
- a ceramic material with increased crystallinity is obtained.
- the crystallinity in the ceramic material may be in the form of alpha-Si - N . , beta-Si 3 N 4 , alpha-SiC, and/or beta-SiC. It has generally been found that the crystallinity of the ceramic material increases with increasing pyrolysis temperature. Therefore, it is preferred that the R 3 SiNH-containing silazane polymer and inorganic compound mixture be fired at a temperature of 1000°C or higher until the mixture is converted to a ceramic material.
- Silazane polymers suitable for use in the present invention are R 3 SiNH-containing silazane polymers.
- R 3 SiNH- containing silazane polymers especially useful in this invention are described in U.S. Patents 4,312,970 and 4,340,619.
- the silazane polymers described in U.S. Patent 4,312,970 are prepared by contacting and reacting in an inert, essentially anhydrous, atmosphere, an organochlorosilane or a mixture of organochlorosilanes of the general formula with a disilazane having the general formula at a temperature in the range of 25°C to 300°C while distilling by-produced volatile products, wherein R' is a vinyl group, an alkyl group of 1-3 carbon atoms, or a phenyl group; R' is a hydrogen atom, a vinyl group, an alkyl group of 1 - 3 carbon atoms, or a phenyl group; and n has a value of 1 or 2.
- organochloromonosilanes of Patent 4,312,970 are those having the general formula where R' is vinyl or an alkyl radical containing 1-3 carbon atoms or the phenyl group.
- R' is vinyl or an alkyl radical containing 1-3 carbon atoms or the phenyl group.
- groups which are contemplated as being useful in this invention are methyl, ethyl, propyl, vinyl and phenyl.
- the R' groups can all be the same or they can be different.
- n 1 or 2.
- the silazane polymers of U.S. Patent 4,340,619 which are the most preferred silazane polymers for the practice of this invention, are prepared by contacting and reacting in an inert, essentially anhydrous, atmosphere, a chlorine-containing disilane or a mixture of chlorine-containing disilanes, of the general formula with a disilazane having the general formula at a temperature in the range of 25°C to 300°C while distilling by-produced volatile products, wherein R' is a vinyl group, an alkyl group of 1 - 3 carbon atoms, or a phenyl group; R' is a hydrogen atom, a vinyl group, an alkyl group of 1 - 3 carbon atoms, or phenyl group; b has a value of 0.5-3; c has a value of 0-2.5; and the sum of (b+c) is equal to three.
- the chlorine-containing disilanes of Patent No. 4,340,619 are those disilanes having the general formula where R' is vinyl, an alkyl radical containing 1 - 3 carbon atoms or the phenyl group.
- the R' groups are methyl, ethyl, propyl, vinyl and phenyl.
- the R' groups can all be the same or they can be different.
- the chlorine-containing disilanes can be those found in the residue from the Direct Process for producing halosilanes (Eaborn, C., "Organosilicon Compounds", Butterworth Scientific Publications, London, 1960, pg. 1).
- the Direct Process is the reaction between silicon metal and aliphatic halides, generally methyl chloride, at elevated temperature in the presence of catalyst, generally copper, to produce chlorosilanes.
- chlorine-containing disilanes For the chlorine-containing disilanes described above, the value of b and c is from 0.5-3 and 0-2.5, respectively, and the sum of (b+c) is equal to three.
- Monosilanes can also be used in admixtures with the above described chlorine-containing disilanes.
- the second reactant in U.S. Patent 4,312,970 and U.S. Patent 4,340,619 is a disilazane of the general formula (R 3 Si) 2 NH.
- R in this formula is vinyl, hydrogen, an alkyl radical of 1-3 carbon atoms or the phenyl group. Therefore, R, for purposes of this formula is represented by hydrogen, methyl, ethyl, propyl, vinyl and phenyl.
- Each R group in this formula can be the same or they can be different.
- Examples of the disilazanes include: and
- inert we mean that the reaction is carried out under a blanket of inert gas, such as argon, nitrogen, or helium.
- inert gas such as argon, nitrogen, or helium.
- essentially anhydrous is that the reaction is preferably carried out in an absolutely anhydrous atmosphere but minute amounts of moisture can be tolerated.
- the mixture is fired to an elevated temperature of at least 750°C until the mixture is converted to a ceramic material. It is generally preferred that the R 3 SiNH-containing silazane polymer and inorganic compound mixture be vacuum stripped prior to pyrolysis. If the silazane polymer and inorganic compound mixture is of sufficient viscosity or it it possesses a sufficiently low melt temperature, it can be shaped first and then pyrolyzed to give a silicon nitride-containing shaped article such as a fiber. The silazane polymer and inorganic compound mixture can be filled with ceramic type fillers (if desired) and then fired to at least 750°C to obtain ceramic materials or ceramic articles.
- the silazane polymer and inorganic compound mixtures of this invention can be used in both the filled and unfilled state, depending on the application.
- Fillers and adjuvants can be milldd on 3 roll mills by simply mixing the polymers and inorganic compounds of this invention with the fillers and making several passes on the mill.
- the polymers and inorganic compounds can be placed in solvents and the fillers and adjuvants can be added thereto and after mixing the solvent can be removed to give the filled polymer mixture.
- the coating can be carried out by conventional means. The means used depends on the polymer mixture and substrates used and the application one has in mind.
- silazane polymer and inorganic compound mixtures of this invention may also be used as an infiltrant with ceramic materials or as a matrix material for composites. Other uses will be apparent to those skilled in the art from a consideration of this specification.
- I. Solution method For inorganic compounds soluble in toluene, a solution method for mixing was generally employed. The desired amount of inorganic compound additive was dissolved in dry toluene. The R 3 SiNH-containing silazane polymer was added to the toluene solution to give a 35 weight percent solution. The resulting solution was placed in a glass jar, purged with argon, and then sealed. The solution was then agitated for 16 hours on a wheel mixer. Solvent was removed from the modified R 3 SiNH-containing silazane by vacuum stripping for three hours at 25°C and 3mm Hg and for one hour at 50°C and 2mm Hg. On occasion, other solvents such as acetone, hexane, or mineral spirits were employed.
- Program D the temperature was raised to 600°C at a rate of 2.8°C/min, raised from 600 to 800°C at a rate of 4°C/min, raised from 800 to 1150°C at a rate of 17.5°C/min, held at 1150°C for 12.4 hours, and then cooled at a rate of 14.4°C/min.
- Program E the temperature was increased to 600°C at a rate of 2.8°C/min, increased from 600 to 800°C at a rate of 3.3°C/min, increased from 800 to 1300°C at the rate of 41.7°C/min, held at 1300°C for 12 minutes, and then cooled at a rate of 36°C/min.
- Program F the temperature was raised to 800°C at a rate of 1.3°C/min, raised from 800 to 1300°C at a rate of 25°C/min, held at 1300°C for 53 minutes, and then cooled at a rate of 49°C/min.
- Program G the temperature was increased to 600°C at a rate of 2.7°C/min, increased from 600 to 800°C at a rate of 0.3°C/min, increased from 800 to 1300°C at a rate of 6.2°C/min, held at 1300°C for 2 hours, and then cooled at 10.8°C/min.
- Program H the temperature was increased to 600°C at a rate of 2.8°C/min, increased from 600 to 800°C at a rate of 6.2°C/min, increased from 800 to 1600°C at a rate of 29.2°C/min, held at 1600°C for 12 minutes, and then cooled at a rate of 44.4°C/min.
- Program I the temperature was increased to 600°C at a rate of 3.0°C/min, increased from 600 to 800°C at a rate of 0.3°C/min. increased from 800 to 1600°C at a rate of 10°C/min, held at 1600°C for 2 hours, and then cooled at a rate of 13.3°C/min.
- Ceramic yield was calculated by dividing the weight after firing by the weight before firing and multiplying the result by 100.
- control samples were subjected to the same treatment (i.e., solution wet milling, or dry milling mixing methods) as the inorganic compound-containing silazane polymers except that the control samples did not contain the inorganic compound.
- the crystallinity of ceramics prepared from control samples subjected to the mixing procedures and control samples not subjected to the mixing procedures was essentially identical.
- a R 3 SiNH-containing silazane polymer prepared by the procedure outlined in U.S. Patent 4,340,619 was employed in this example.
- hexamethyldisilazane (42.2 pounds) and a mixture of methyl- chlorodisilanes (26 pounds) were combined under a nitrogen atmosphere.
- the methylcholordisilane mixture obtained from the Direct Process, contained 42.5 weight percent [(CH 3 )Cl 2 Si] 2 , 35.6 weight percent (CH 3 ) 2 ClSiSiCl 2 (CH 3 ), 9.5 weight percent [(CH 3 ) 2 ClSi] 2 , and 12.4 weight percent of chlorosilane low boilers.
- the reaction mixture was heated to 195°C under nitrogen at a rate of 0.97°C/min while volatile by-products were removed by distillation. The polymer residue was collected and was found to have a softening point of 68°C.
- This example shows the use of various iron compounds as crystallinity enhancing additives.
- the same R 3 SiNH-containing silazane polymer as described in Example 1 was used.
- the amount of additive used was such that the resulting modified silazane polymer contained 1.0 percent by weight iron.
- All additives, except iron oxide, were mixed with the silazane polymer using the solution method. Iron oxide was added using the dry milling technique. All samples were then fired to 1300°C under helium using temperature program E. Fired samples were examined by x-ray diffraction. The results are presented in Table II.
- This example shows the use of an iron (III) octoate crystallinity enhancing agent at various additive levels.
- the same R 3 SiNH-containing silazane polymer as described in Example 1 was employed. Additives were incorporated into the silazane polymer using either the solution or wet milling technique. After mixing the additive into the silazane polymer, the silazane polymer was fired at 1300°C under helium using temperature program E. The ceramic products were examined by x-ray diffraction. The results are presented in Table III. The x-ray diffraction peaks for the ceramic material from the 0.1 percent iron containing silazane polymer were not well defined. Ceramic materials prepared from the other iron containing silazane polymers gave well defined x-ray diffraction peaks corresponding to the noted crystalline phases.
- This example shows the preparation of ceramic material by firing iron (III) octoate containing silazane polymers under varying pyrolysis temperatures and conditions.
- the R 3 SiNH-containing silazane polymer described in Example 1 was used.
- Iron (III) octoate was incorporated into the silazane polymer at a level equivalent to 1.0 weight percent iron using the wet milling method.
- the ceramic material was examined by x-ray diffraction. The results are presented in Table IV. All samples were fired in a helium atmosphere.
- This example gives quantative x-ray diffraction data for ceramic materials prepared from R 3 SiNH-containing silazane polymer with and without iron additives.
- the R 3 SiNH-containing silazane polymer was the same as used in Example 1.
- the iron additives were incorporated into the silazane polymer at levels sufficient to give 1.0 weight percent iron using the wet milling technique.
- the additives employed were iron (III) oxide and iron (III) octoate. Samples were fired under helium using various firing conditions. The resulting ceramic materials were then examined by quantitative x-ray diffraction. The results are presented in Table V.
- This example shows the preparation of ceramic fibers using the process of this invention.
- the R 3 SiNH- containing silazane polymer of Example 1 was employed.
- the inorganic compounds were incorporated into the R 3 SiNH- containing silazane polymer at levels to give 1.0 weight percent of the metal using the wet milling technique.
- a melt rheometer equipped with a 3/8 inch barrel was employed to prepare fibers from silazane polymers containing nickel (II) octoate and cobalt (II) octoate as well as the control (no additive). Fiber from a silazane polymer containing iron (III) octoate were prepared on an extruder equipped with a 10 micron spinning head.
- Fibers were cured for 3 hours at 80°C in air prior to firing. The fibers were then fired under helium at 1300°C using Program F except for the control fibers which were fired under helium at 1300°C using Program E. The fired ceramic fibers were then ground in a mortar and pestle and examined by x-ray diffraction. The results are presented in Table VI.
- This example shows the use of mixtures of crystallinity enhancing additives.
- the R 3 SiNH-containing silazane polymer of Example 1 was employed.
- a mixture of the R 3 SiNH-containing silazane polymer containing 0.5 weight percent nickel and 0.5 percent iron was prepared by the wet milling method using nickel (II) octoate and iron (III) octoate as the additives.
- the modified silazane polymer was fired under helium to 1300°C using Program E.
- a ceramic material 53.0 percent ceramic yield) was obtained which contained a-SiC and a-Si3N 4 by X-ray diffraction.
- R 3 SiNH-containing silazane polymer which contained 0.5 weight percent copper and 0.5 weight percent iron was also prepared by the wet milling technique using copper (II) octoate and iron (III) octoate.
- the modified silazane polymer was fired to 1300°C under helium using Program E.
- a ceramic material (65.3 percent ceramic yield) was obtained which contained a-SiC and ⁇ -Si3N4 as crystalline phases.
- the R 3 SiNH-containing silazane polymer of Example 1 was used. Numerous inorganic compounds or metals were evaluated as crystallinity enhancing agents. The general procedures of Examples 1 - 7 were used. The additives were incorporated into the R 3 SiNH-containing polymer at a level of about 1 weight percent of the element and, thereafter, the modified silazane polymers were fired at an elevated temperature in the range of 1000 - 1600°C under an inert atmosphere. The resulting ceramic materials were then examined by x-ray diffraction. The additives examined are listed in Table VII. None of the listed additives were found to enhance crystallinity to any significant extent. Most of the resulting ceramic materials were amorphous.
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Abstract
Description
- This invention relates to the preparation of ceramic materials with increased crystallinity. More specifically, this invention relates to the preparation of ceramic materials with increased levels of crystalline SiC and/or Si3N4. The ceramic materials of this invention are obtained by firing a mixture of a R3SiNH-containing silazane polymer and certain inorganic compounds to an elevated temperature in an inert atmosphere or in a vacuum. The additives that allow for ceramic materials with increased crystallinity include iron compounds, cobalt compounds, nickel compounds, and copper compounds.
- Ceramic material prepared from R3SirlH-containing silazane polymers are known to the art. Gaul, in U.S. Patent No. 4,340,619 (issued July 20, 1982), prepared ceramic materials by firing at elevated temperatures in an inert atmosphere a R3SiNH-containing silazane polymer prepared by contacting and reacting, in an inert, essentially anhydrous atmosphere, chlorine-containing disilanes with disilazanes. The ceramic material of U.S. Patent No. 4,340,619 contained crystalline SiC and/or Si3N4 only when the R3SiNH-containing silazane polymer was fired to at least 1600°C.
- Gaul in U.S. Patent 4,312,970, issued January 26, 1984, obtained ceramics by firing a R3SiNH-containing silazane polymer, prepared by contacting and reacting an organochlorosilane with a disilazane, at elevated temperatures in an inert atmosphere or in a vacuum. The crystalline content of the ceramic materials was not reported.
- What is newly discovered is that certain inorganic compounds when added to R3SiNH-containing silazane polymer prior to firing at elevated temperatures, allow for the formation of ceramic materials with increased crystallinity relative to ceramic materials fired under the same conditions without the additives. The process of this invention allows for the formation of ceramic materials with increased levels of crystalline Si3N4 and/or SiC. The process of this invention also allows for the formation of ceramic materials containing crystalline Si3N4 and/or SiC at lower pyrolysis temperatures.
- This invention relates to a method of preparing a ceramic material with increased crystallinity, said method comprising heating a modified R3SiNH-containing silizane polymer in an inert atmosphere or in a vacuum to a temperature of at least 750°C until said modified R3SiNH-containing silazane polymer is converted to a ceramic material with increased crystallinity relative to a non-modified R3SiNH-containing silazane polymer heated under the same conditions, wherein said modified R3SiNH-containing silazane polymer is prepared by mixing the non-modified R3SiNH-containing silazane polymer with an effective, crystallinity increasing, amount of an inorganic compound selected from the group consisting of iron compounds, cobalt compounds, nickel compounds, and copper compounds.
- The process of this invention is carried out by first mixing a R3SiNH-containing silazane polymer with an effective amount of an inorganic compound and then firing the resulting mixture to an elevated temperature under an inert atmosphere or in a vacuum until the resulting mixture is converted to a ceramic material. Suitable inorganic additives for the practice of the invention include iron compounds, cobalt compounds, nickel compounds, and copper compounds. These inorganic compounds include organometallic compounds as detailed below.
- Suitable iron compounds include iron (II) compounds, iron (III) compounds and zero valence iron compounds. Examples of suitable iron compounds include iron (II) bromide, iron (III) bromide, iron (II) ethylenedi- ammonium sulfate, iron (II) oxalate, iron (III) octoate, iron (II) acetate, iron (III) acetate hydroxide, disodium tetracarbonylferrate, sodium pentacyanonitrosylferrate (III), pentacarbonyliron, ammonium trioxalatoferrate (III), ammonium hexacyanoferrate (II), potassium hexacyanoferrate (III), potassium trioxalatoferrate (III), potassium hexacyanoferrate (II), dicarbonylcyclopentadienyliodoiron, butadienetricarbonyliron, bis(cyclopentadienyl)iron, iron (II) acetylacetonate, ferrocene carbaldehyde, ferrocene carboxylic acid, ferrocene dicarboxylic acid, 1,1-dimethylferrocene, iron (II) gluconate, (dimethylamino methyl) ferrocene, n-butylferrocene, t-butyl ferrocene, iron (III) acetylacetonate, ferrocenyl phenyl ketone, iron (III) 2-ethylhexanoate, iron (II) chloride, iron (II) perchlorate, iron (III) chloride, iron (III) perchlorate, iron (II) fluoride, iron (III) fluoride, sodium hexafluoroferrate (III), ammonium iron (III) sulfate, ammonium iron (II) sulfate, iron (II) iodide, iron (III) nitrate, iron (II) oxide, iron (III) phosphate, iron (II) sulfate, iron (III) oxalate, nonacarbonyldiiron, tris(ethylenediamine)iron (III) sulfate, bis[dicarbonyl(methylcyclopentadenyl)iron], copper diiron tetraoxide, diiron nickel tetraoxide, iron (III) oxide, iron (III) sulfate, iron carbide, dodecacarbonyltriiron, iron (II) phosphate, iron nitride, and the like. Preferred iron compounds include iron (III) octoate, iron (III) oxide, iron (II) acetylacetonate, iron (III) chloride and nonocarbonyl diiron.
- Suitable cobalt compounds include cobalt (II) compounds, cobalt (III) compounds, cobalt (IV) compounds, and zero valence cobalt compounds. Examples of suitable cobalt compounds include cobalt (II) tetrafluoroborate, cobalt (II) borate, cobalt (II) bromide, cobalt (II) carbonate, cobalt (II) thiocyanate, cobalt (II) oxalate, tricarbonylnitrosyl cobalt, cobalt (II) acetate, tris(ethylenediamine) cobalt (III) chloride, tris(ethylenediamine) cobalt (II) sulfate, potassium hexacyanocobaltate (III), cobalt (II) octoate, dicarbonylcyclopentadienyl cobalt, bis(cyclopentadienyl) cobalt, cobalt (II) acetylacetonate, cobalt (II) benzoate, cobalt (III) acetylacetonate, N,N'-bis(salicylidene) ethylenediimino cobalt (II), cobalt (II) cyclohexanebutyrate, cobalt (II) chloride, cobalt (II) perchlorate, penta- aminechloro cobalt (III) chloride, pentaamineaquocobalt (III) chloride, hexaamine cobalt (III) chloride, cobalt (II) fluoride, cobalt (III) "fluoride, cobalt diiron tetraoxide, cobalt (II) hydroxide, cobalt (II) iodide, cobalt (II) nitrate, sodium hexanitritocobaltate (III), cobalt (II) oxide, cobalt (II) sulfate, cobalt (IV) sulfide, octacarbonyldicobalt, and the like. A preferred cobalt compound is cobalt (II) octoate.
- Suitable nickel compounds include nickel (II) compounds, nickel (III) compounds, nickel (IV) compounds, and zero valence nickel compounds. Examples of suitable nickel compounds include nickel boride, nickel tetrafluoroborate, nickel (II) bromide, nickel (II) carbonate, nickel (II) oxalate, nickel (II) acetate, tetracarbonyl nickel, tri(ethylenediamine) nickel (II) sulfate, bis(cyclopentadienyl) nickel, nickel (II) acetoacetonate, bis(triethylphosphine) nickel (II) chloride, nickel (II) n-phenyl- glycinate, nickel (II) 2-ethylhexanoate, nickel cyclohexanebutyrate, nickel (II) chloride, nickel (II) perchlorate, nickel (II) fluoride, potassium hexafluoronickelate (IV), nickel hexafluorosilicate, diiron nickel tetraoxide, nickel (II) hydroxide, nickel (II) octoate, nickel sulfonate, ammonium nickel sulfate, nickel (II) iodide, nickel (II) nitrate, nickel (II) oxide, nickel (II) sulfate, nickel (II) sulfide, nickel (IV) sulfide, nickel (III) oxide, nickel phosphide, and the like. A preferred nickel compound is nickel (II) octoate.
- Suitable copper compounds include copper (I) compounds and copper (II) compounds. Examples of suitable copper compounds include copper (II) tetrafluoroborate, copper (I) bromide, copper (II) bromide, copper (I) cyanide, copper (I) thiocyanate, copper (I) acetate, copper (II) acetate, copper (II) octoate, copper (I) t-butoxide, copper thiophenoxide, tri(ethylenediamine) copper (II) sulfate, disodium salt of ethylenediamine-tetraacetic acid copper (II), copper (II) acetylacetonate, copper (II) octoate, copper (II) gluconate, copper salt of acetylsalicylic acid, copper (II) cyclohexanebutyrate, copper '(I) chloride, copper (II) chloride, copper (II) perchlorate, copper (II) chromite, copper (II) fluoride, copper diiron tetraoxide, copper (II) hydroxide, copper (I) iodide, copper (I) iodate, copper (II) nitrate, copper (II) oxide, copper (II) sulfate, copper (III) sulfide, copper (II) carbonate dihydroxide, copper (I) oxide, copper (I) sulfide, copper (I) nitride, copper (I) phosphide, and the like. A preferred copper compound is copper (II) octoate.
- Mixture of various iron compounds, cobalt compounds, nickel compounds, and copper compounds may also be employed.
- As one skilled in the art would realize, not all combinations of R3SiNH-containing silazane polymers, the just listed compounds, and pyrolysis conditions will lead to ceramic materials with increased crystallinity. Routine experimentation may be required in some cases to determine if an increase in crystallinity is actually realized. Cases where such an increase in crystallinity is not realized are not, naturally, considered to be within the stope of this invention.
- The method of mixing the R3SiNH-containing silazane polymer and the inorganic compound is not critical. It is preferred that the R3SiNH-containing silazane polymer and the inorganic compound be well mixed in order to obtain ceramic materials or articles where the amount of crystalline Si3N4 and/or SiC does not vary appreciably throughout the ceramic material or article. Using an organic solvent such a toluene helps to insure that the two components are well mixed. When a solvent is employed to mix the R3SiNH-containing.silazane polymer and the inorganic material, the solvent should be removed by conventional means prior to heating the mixture to an elevated temperature in order form a ceramic material. The R3SiNH-containing silazane polymer and the inorganic compounds may also be mixed on 3 roll mills by simply adding the ingredients and making several passes on the mill. As will be apparent to one of ordinary skill in the art, other mixing techniques may be used that will result in ceramic materials or articles with the level of crystallinity uniform throughout the ceramic material or article.
- The R3SiNH-containing silazane polymer is mixed with an effective amount of an inorganic compound. By "an effective amount" of the inorganic compound we mean that amount which results in increased crystallinity in the resulting ceramic material. Generally the inorganic compound is added at such a level so as to obtain a mixture containing the R3SiNH-containing silazane polymer and about 0.1 to 2.0 weight percent of the metal associated with the inorganic compound. The inorganic compound may be added at higher levels although no added benefits are noted. The increase in crystallinity of the ceramic material of this invention is measured by comparison with the crystallinity of a ceramic material obtained by firing the same R3SiNH-containing silazane polymer, without any added inorganic compounds, under the same experimental conditions.
- The mixture of R3SiNH-containing silazane polymer and an effective amount of an inorganic compound is fired to elevated temperatures of at least 750°C under an inert atmosphere or in a vacuum until the mixture is converted to a ceramic material. A ceramic material with increased crystallinity is obtained. The crystallinity in the ceramic material may be in the form of alpha-Si-N., beta-Si3N4, alpha-SiC, and/or beta-SiC. It has generally been found that the crystallinity of the ceramic material increases with increasing pyrolysis temperature. Therefore, it is preferred that the R3SiNH-containing silazane polymer and inorganic compound mixture be fired at a temperature of 1000°C or higher until the mixture is converted to a ceramic material.
- Although not wishing to be limited by theory, we believe that during pyrolysis the inorganic compounds are reduced to the metal and that, perhaps, the metal derived from the inorganic compound, in intimate contact on the atomic level with the components of the mixture, is responsible for the increase in crystallinity. Adding the metal alone does not seem to increase the crystallinity of the ceramic material, perhaps, because it is difficult to obtain intimate contact between the metal and other reactants. The in-situ formation of the metal by reduction of the inorganic compound during pyrolysis may insure intimate contact on a atomic or molecular level.
- Silazane polymers suitable for use in the present invention are R3SiNH-containing silazane polymers. R3SiNH- containing silazane polymers especially useful in this invention are described in U.S. Patents 4,312,970 and 4,340,619.
- The silazane polymers described in U.S. Patent 4,312,970 are prepared by contacting and reacting in an inert, essentially anhydrous, atmosphere, an organochlorosilane or a mixture of organochlorosilanes of the general formula
with a disilazane having the general formula
at a temperature in the range of 25°C to 300°C while distilling by-produced volatile products, wherein R' is a vinyl group, an alkyl group of 1-3 carbon atoms, or a phenyl group; R' is a hydrogen atom, a vinyl group, an alkyl group of 1 - 3 carbon atoms, or a phenyl group; and n has a value of 1 or 2. - The organochloromonosilanes of Patent 4,312,970 are those having the general formula
where R' is vinyl or an alkyl radical containing 1-3 carbon atoms or the phenyl group. Thus, those groups which are contemplated as being useful in this invention are methyl, ethyl, propyl, vinyl and phenyl. The R' groups can all be the same or they can be different. - The value of n is 1 or 2. Thus, single organic group substituted silanes such as CH3SiCl3, C6H5SiCl3, CH2 =CHSiCI3, CH3CH2SiCl3 or CH3(CH2)2SiCl3 and double organic group substituted silanes such as (CH3)2SiCl2, (C2H5)2SiCl2 and (CH2=CH)(CH3)SiCl2 and mixtures of such silanes, for example, CH3SiC13 and (CH3)2SiCl2, can be used. It is preferred that when organochlorosilane mixtures are used, the number of units of diorgano-substituted silicon atoms should not exceed the number of units of monoorgano-substituted silicon atoms.
- The silazane polymers of U.S. Patent 4,340,619 which are the most preferred silazane polymers for the practice of this invention, are prepared by contacting and reacting in an inert, essentially anhydrous, atmosphere, a chlorine-containing disilane or a mixture of chlorine-containing disilanes, of the general formula
with a disilazane having the general formula
at a temperature in the range of 25°C to 300°C while distilling by-produced volatile products, wherein R' is a vinyl group, an alkyl group of 1 - 3 carbon atoms, or a phenyl group; R' is a hydrogen atom, a vinyl group, an alkyl group of 1 - 3 carbon atoms, or phenyl group; b has a value of 0.5-3; c has a value of 0-2.5; and the sum of (b+c) is equal to three. - The chlorine-containing disilanes of Patent No. 4,340,619 are those disilanes having the general formula
where R' is vinyl, an alkyl radical containing 1 - 3 carbon atoms or the phenyl group. Thus, the R' groups are methyl, ethyl, propyl, vinyl and phenyl. The R' groups can all be the same or they can be different. The chlorine-containing disilanes can be those found in the residue from the Direct Process for producing halosilanes (Eaborn, C., "Organosilicon Compounds", Butterworth Scientific Publications, London, 1960, pg. 1). The Direct Process is the reaction between silicon metal and aliphatic halides, generally methyl chloride, at elevated temperature in the presence of catalyst, generally copper, to produce chlorosilanes. - For the chlorine-containing disilanes described above, the value of b and c is from 0.5-3 and 0-2.5, respectively, and the sum of (b+c) is equal to three. Examples of chlorine-containing disilanes are [C1(CH3)2Si]2, [Cl2(CH3)Si]2, [Cl2(C2H5)Si]2, [Cl(C6H5)2Si]2, and [Cl2(CH2=CH)Si]2.
- Monosilanes can also be used in admixtures with the above described chlorine-containing disilanes. Examples include CH3SiCl3, (CH3)2SiC12, H(CH3)2SiCl, (CH3)3SiCl, (CH2=CH)(CH3)2SiCl, (C2H5)2SiCl2, C6H5SiCl3, as well as (C6H5)2SiCl2, and (C6H5)3SiCl.
- When polysilazane polymers are prepared in accordance with Patent 4,340,619 for use in this invention, it is preferred that mixtures of chlorine-containing disilanes be employed where the number of units of diorgano-substituted silicon atoms does not exceed the number of units of monoorgano-substituted silicon atoms.
- The second reactant in U.S. Patent 4,312,970 and U.S. Patent 4,340,619 is a disilazane of the general formula (R3Si)2NH. R in this formula is vinyl, hydrogen, an alkyl radical of 1-3 carbon atoms or the phenyl group. Therefore, R, for purposes of this formula is represented by hydrogen, methyl, ethyl, propyl, vinyl and phenyl. Each R group in this formula can be the same or they can be different. Examples of the disilazanes include:
- These reactants are brought together in an inert, essentially anhydrous atmosphere. By "inert", we mean that the reaction is carried out under a blanket of inert gas, such as argon, nitrogen, or helium. What we mean by "essentially anhydrous" is that the reaction is preferably carried out in an absolutely anhydrous atmosphere but minute amounts of moisture can be tolerated.
- When the reactants are contacted with each other, as described in Patents 4,312,970 and 4,340,619 the reaction begins which forms an intermediate amino compound. Upon heating, additional amino compound is formed and upon continued heating, R3SiCl is distilled from the reaction mixture and a silazane polymer is formed. The order of addition of the materials does not appear to be critical. As the temperature is raised higher, more condensation takes place and cross-linking occurs with residual R3Si- that is not distilled from the mixture acting as a chain-stopper. This control allows one to stop the reaction at any point to obtain almost any desired viscosity. The desirable temperature range for this reaction is 25°C to 300°C. A preferred temperature range for this reaction is 125° - 300°C. The length of time that the reaction requires depends on.the temperature employed and the viscosity one wishes to achieve.
- What is meant by "volatile products" are the distillable by-produced products that are formed by the reactions set forth above. These materials can be represented by (CH3)3SiCl, (CH=CH)(C6H5)2SiCl, CH3(C6H5)2SiCl, (CH3)2C6H5SiCl and (CH2=CH)(CH3)2SiCl. Sometimes, the process requires the use of a vacuum along with the heat in order to remove these materials from the reaction mixture.
- Afte'r the R3SiNH-containing silazane polymer and the inorganic compound are mixed, the mixture is fired to an elevated temperature of at least 750°C until the mixture is converted to a ceramic material. It is generally preferred that the R3SiNH-containing silazane polymer and inorganic compound mixture be vacuum stripped prior to pyrolysis. If the silazane polymer and inorganic compound mixture is of sufficient viscosity or it it possesses a sufficiently low melt temperature, it can be shaped first and then pyrolyzed to give a silicon nitride-containing shaped article such as a fiber. The silazane polymer and inorganic compound mixture can be filled with ceramic type fillers (if desired) and then fired to at least 750°C to obtain ceramic materials or ceramic articles.
- The silazane polymer and inorganic compound mixtures of this invention can be used in both the filled and unfilled state, depending on the application. Thus, it is contemplated within the scope of this invention to coat substrates with filled and unfilled mixtures and heat the substrates to produce ceramic coated articles. Fillers and adjuvants can be milldd on 3 roll mills by simply mixing the polymers and inorganic compounds of this invention with the fillers and making several passes on the mill. In the alternative, the polymers and inorganic compounds can be placed in solvents and the fillers and adjuvants can be added thereto and after mixing the solvent can be removed to give the filled polymer mixture. The coating can be carried out by conventional means. The means used depends on the polymer mixture and substrates used and the application one has in mind. Thus, these materials can be brushed, rolled, dipped or sprayed. In the filled state, it is sometimes necessary to trowel the mixture onto the substrate. The silazane polymer and inorganic compound mixtures of this invention may also be used as an infiltrant with ceramic materials or as a matrix material for composites. Other uses will be apparent to those skilled in the art from a consideration of this specification.
- So that those skilled in the art can better appreciate and understand the invention, the following examples are given.
- In the examples, three basic mixing techniques were employed to mix the R3SiNH-containing silazane polymer and the inorganic compounds.
- I. Solution method. For inorganic compounds soluble in toluene, a solution method for mixing was generally employed. The desired amount of inorganic compound additive was dissolved in dry toluene. The R3SiNH-containing silazane polymer was added to the toluene solution to give a 35 weight percent solution. The resulting solution was placed in a glass jar, purged with argon, and then sealed. The solution was then agitated for 16 hours on a wheel mixer. Solvent was removed from the modified R3SiNH-containing silazane by vacuum stripping for three hours at 25°C and 3mm Hg and for one hour at 50°C and 2mm Hg. On occasion, other solvents such as acetone, hexane, or mineral spirits were employed.
- For inorganic compounds insoluble in toluene, one of the two following methods were employed.
- II. Wet milling method. The required amount of inorganic compound was added to a 50 weight percent solution of the R3SiNH-containing silazane polymer in dry toluene in a half-pint mill jar. After adding ceramic milling balls, the jar was purged with argon and sealed. The sample was wet milled for 16 hours. The solvent was removed as in the solution method. On occasion, other solvents such as acetone, hexane, or mineral spirits were used.
- III. Dry milling method. The required amount inorganic compound was added to powdered R3SiNH-containing silazane polymer in a half-pint milling jar. The silazane polymer had been powdered in a mortar and pestle. After the addition of ceramic milling balls, the milling jar was purged with argon and sealed. The sample was milled for 16 hours.
- All mixed samples were stored under argon in a dry box until used.
- All samples were fired under a helium atmosphere in an Astro Industries Furnace 1000A water cooled graphite heated model 1000.3060-FP-12 equipped with a model 5300 Data Trak Temperature Programmer. The following temperature programs were employed for firing. Using Program A, the temperature was raised to 600°C at a rate of 2.8°C/min, raised from 600 to 800°C at a rate of 3.3°C/min, raised from 800 to 900°C at a rate of 8.3°C/min, held at 900°C for 12 minutes and then cooled at a rate of 25°C/min. With Program B, the temperature was increased to 600°C at a rate of 2.9°C/min, increased from 600 to 900°C at a rate of 3.8°C/min, held at 900°C for 12.4 hours, then cooled at a rate of 11.2°C/min. With Program C, the temperature was raised to 600°C at a rate of 2.8°C/min, raised from-600 to 800°C at a rate of 3.3°C/min, raised from 800 to 1000°C at a rate of 16.7°C/min, held at 1000°C for 24 minutes, and then cooled at a rate of 41.7°C/min. Using Program D, the temperature was raised to 600°C at a rate of 2.8°C/min, raised from 600 to 800°C at a rate of 4°C/min, raised from 800 to 1150°C at a rate of 17.5°C/min, held at 1150°C for 12.4 hours, and then cooled at a rate of 14.4°C/min. In Program E, the temperature was increased to 600°C at a rate of 2.8°C/min, increased from 600 to 800°C at a rate of 3.3°C/min, increased from 800 to 1300°C at the rate of 41.7°C/min, held at 1300°C for 12 minutes, and then cooled at a rate of 36°C/min. With Program F, the temperature was raised to 800°C at a rate of 1.3°C/min, raised from 800 to 1300°C at a rate of 25°C/min, held at 1300°C for 53 minutes, and then cooled at a rate of 49°C/min. Using Program G, the temperature was increased to 600°C at a rate of 2.7°C/min, increased from 600 to 800°C at a rate of 0.3°C/min, increased from 800 to 1300°C at a rate of 6.2°C/min, held at 1300°C for 2 hours, and then cooled at 10.8°C/min. With Program H, the temperature was increased to 600°C at a rate of 2.8°C/min, increased from 600 to 800°C at a rate of 6.2°C/min, increased from 800 to 1600°C at a rate of 29.2°C/min, held at 1600°C for 12 minutes, and then cooled at a rate of 44.4°C/min. Using Program I, the temperature was increased to 600°C at a rate of 3.0°C/min, increased from 600 to 800°C at a rate of 0.3°C/min. increased from 800 to 1600°C at a rate of 10°C/min, held at 1600°C for 2 hours, and then cooled at a rate of 13.3°C/min.
- Both qualitative and quantitative X-ray diffraction determinations were made on the ceramic materials. Quantitative X-ray diffraction determinations were made using the procedure outlined in L. K. Frevel and W. C. Roth, Anal. Chem., 54, 677-682 (1982). Qualitative X-ray diffraction determinations were carried out using standard procedures. For the qualitative work it was not possible to identify 6-SiC in the presence of a-SiC with certainity because the X-ray diffraction peaks of a-SiC overlap the peaks of a-SiC. All ceramic materials produced by the method of this invention which were examined by the quantitative method contained both a-SiC and β-SiC (see Example 5). It seems likely, therefore, that the ceramics prepared by the method of this invention which were only examined by qualitative X-ray diffraction also contained both a-SiC and 6-SiC. However, because of the limitations of the method, only a-SiC could be positively identified.
- Ceramic yield was calculated by dividing the weight after firing by the weight before firing and multiplying the result by 100.
- In the examples, control samples were subjected to the same treatment (i.e., solution wet milling, or dry milling mixing methods) as the inorganic compound-containing silazane polymers except that the control samples did not contain the inorganic compound. The crystallinity of ceramics prepared from control samples subjected to the mixing procedures and control samples not subjected to the mixing procedures was essentially identical.
- A R3SiNH-containing silazane polymer prepared by the procedure outlined in U.S. Patent 4,340,619 was employed in this example. In a 72 liter stainless steel reactor, hexamethyldisilazane (42.2 pounds) and a mixture of methyl- chlorodisilanes (26 pounds) were combined under a nitrogen atmosphere. The methylcholordisilane mixture, obtained from the Direct Process, contained 42.5 weight percent [(CH3)Cl2Si]2, 35.6 weight percent (CH3)2ClSiSiCl2(CH3), 9.5 weight percent [(CH3)2ClSi]2, and 12.4 weight percent of chlorosilane low boilers. The reaction mixture was heated to 195°C under nitrogen at a rate of 0.97°C/min while volatile by-products were removed by distillation. The polymer residue was collected and was found to have a softening point of 68°C.
- Several different inorganic compounds were added to the R3SiNH-containing silazane polymer at levels to yield a 1 percent by weight, based on the metal, mixture. The additives used were iron (III) octoate, cobalt (II) octoate, copper (II) octoate, and nickel (II) octoate. All were mixed using the solution method with toluene as the solvent. A control sample, which contained no additives, was also subjected to the same procedure. All samples were then fired to 1300°C under helium using temperature program E. After firing all samples were examined by x-ray diffraction.
- This example shows the use of various iron compounds as crystallinity enhancing additives. The same R3SiNH-containing silazane polymer as described in Example 1 was used. The amount of additive used was such that the resulting modified silazane polymer contained 1.0 percent by weight iron. All additives, except iron oxide, were mixed with the silazane polymer using the solution method. Iron oxide was added using the dry milling technique. All samples were then fired to 1300°C under helium using temperature program E. Fired samples were examined by x-ray diffraction. The results are presented in Table II.
- This example shows the use of an iron (III) octoate crystallinity enhancing agent at various additive levels. The same R3SiNH-containing silazane polymer as described in Example 1 was employed. Additives were incorporated into the silazane polymer using either the solution or wet milling technique. After mixing the additive into the silazane polymer, the silazane polymer was fired at 1300°C under helium using temperature program E. The ceramic products were examined by x-ray diffraction. The results are presented in Table III. The x-ray diffraction peaks for the ceramic material from the 0.1 percent iron containing silazane polymer were not well defined. Ceramic materials prepared from the other iron containing silazane polymers gave well defined x-ray diffraction peaks corresponding to the noted crystalline phases.
- This example shows the preparation of ceramic material by firing iron (III) octoate containing silazane polymers under varying pyrolysis temperatures and conditions. The R3SiNH-containing silazane polymer described in Example 1 was used. Iron (III) octoate was incorporated into the silazane polymer at a level equivalent to 1.0 weight percent iron using the wet milling method. After firing, the ceramic material was examined by x-ray diffraction. The results are presented in Table IV. All samples were fired in a helium atmosphere.
- This example gives quantative x-ray diffraction data for ceramic materials prepared from R3SiNH-containing silazane polymer with and without iron additives. The R3SiNH-containing silazane polymer was the same as used in Example 1. The iron additives were incorporated into the silazane polymer at levels sufficient to give 1.0 weight percent iron using the wet milling technique. The additives employed were iron (III) oxide and iron (III) octoate. Samples were fired under helium using various firing conditions. The resulting ceramic materials were then examined by quantitative x-ray diffraction. The results are presented in Table V.
- This example shows the preparation of ceramic fibers using the process of this invention. The R3SiNH- containing silazane polymer of Example 1 was employed. The inorganic compounds were incorporated into the R3SiNH- containing silazane polymer at levels to give 1.0 weight percent of the metal using the wet milling technique. A melt rheometer equipped with a 3/8 inch barrel was employed to prepare fibers from silazane polymers containing nickel (II) octoate and cobalt (II) octoate as well as the control (no additive). Fiber from a silazane polymer containing iron (III) octoate were prepared on an extruder equipped with a 10 micron spinning head. Fibers were cured for 3 hours at 80°C in air prior to firing. The fibers were then fired under helium at 1300°C using Program F except for the control fibers which were fired under helium at 1300°C using Program E. The fired ceramic fibers were then ground in a mortar and pestle and examined by x-ray diffraction. The results are presented in Table VI.
- This example shows the use of mixtures of crystallinity enhancing additives. The R3SiNH-containing silazane polymer of Example 1 was employed. A mixture of the R3SiNH-containing silazane polymer containing 0.5 weight percent nickel and 0.5 percent iron was prepared by the wet milling method using nickel (II) octoate and iron (III) octoate as the additives. The modified silazane polymer was fired under helium to 1300°C using Program E. A ceramic material (53.0 percent ceramic yield) was obtained which contained a-SiC and a-Si3N4 by X-ray diffraction.
- Another R3SiNH-containing silazane polymer which contained 0.5 weight percent copper and 0.5 weight percent iron was also prepared by the wet milling technique using copper (II) octoate and iron (III) octoate. The modified silazane polymer was fired to 1300°C under helium using Program E. A ceramic material (65.3 percent ceramic yield) was obtained which contained a-SiC and α-Si3N4 as crystalline phases.
- This example is included for comparison only. The R3SiNH-containing silazane polymer of Example 1 was used. Numerous inorganic compounds or metals were evaluated as crystallinity enhancing agents. The general procedures of Examples 1 - 7 were used. The additives were incorporated into the R3SiNH-containing polymer at a level of about 1 weight percent of the element and, thereafter, the modified silazane polymers were fired at an elevated temperature in the range of 1000 - 1600°C under an inert atmosphere. The resulting ceramic materials were then examined by x-ray diffraction. The additives examined are listed in Table VII. None of the listed additives were found to enhance crystallinity to any significant extent. Most of the resulting ceramic materials were amorphous.
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US652939 | 1984-09-21 |
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Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0184123A2 (en) * | 1984-12-04 | 1986-06-11 | Dow Corning Corporation | Ceramic materials from polycarbosilanes |
US4870035A (en) * | 1986-06-10 | 1989-09-26 | Shin-Etsu Chemical Co., Ltd. | Process for manufacturing organic silazane polymers and process for manufacturing ceramics from the polymers |
US5952421A (en) * | 1995-12-27 | 1999-09-14 | Exxon Research And Engineering Co. | Synthesis of preceramic polymer-stabilized metal colloids and their conversion to microporous ceramics |
CN100506891C (en) * | 2006-03-24 | 2009-07-01 | 中国科学院化学研究所 | Preparation method of iron containing polysilazane |
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SU338424A1 (en) * | А. В. Иванова, Л. Н. Жинкина, В. В. Филатов, Д. Я. Жинкин, М. В. Соболевский , А. П. Некрасов | JS.COM. J ....... ACCH'NL • j'r'f'l • '- "\ -: 1M (' imjvshash ^; LO"> & L1 | ||
US4482689A (en) * | 1984-03-12 | 1984-11-13 | Dow Corning Corporation | Process for the preparation of polymetallo(disily)silazane polymers and the polymers therefrom |
-
1985
- 1985-07-29 CA CA000487697A patent/CA1242461A/en not_active Expired
- 1985-09-20 DE DE8585111950T patent/DE3572165D1/en not_active Expired
- 1985-09-20 JP JP60208534A patent/JPS6177611A/en active Granted
- 1985-09-20 EP EP85111950A patent/EP0175384B1/en not_active Expired
Patent Citations (2)
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SU338424A1 (en) * | А. В. Иванова, Л. Н. Жинкина, В. В. Филатов, Д. Я. Жинкин, М. В. Соболевский , А. П. Некрасов | JS.COM. J ....... ACCH'NL • j'r'f'l • '- "\ -: 1M (' imjvshash ^; LO"> & L1 | ||
US4482689A (en) * | 1984-03-12 | 1984-11-13 | Dow Corning Corporation | Process for the preparation of polymetallo(disily)silazane polymers and the polymers therefrom |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0184123A2 (en) * | 1984-12-04 | 1986-06-11 | Dow Corning Corporation | Ceramic materials from polycarbosilanes |
EP0184123A3 (en) * | 1984-12-04 | 1988-01-07 | Dow Corning Corporation | Ceramic materials from polycarbosilanes |
US4870035A (en) * | 1986-06-10 | 1989-09-26 | Shin-Etsu Chemical Co., Ltd. | Process for manufacturing organic silazane polymers and process for manufacturing ceramics from the polymers |
US5952421A (en) * | 1995-12-27 | 1999-09-14 | Exxon Research And Engineering Co. | Synthesis of preceramic polymer-stabilized metal colloids and their conversion to microporous ceramics |
CN100506891C (en) * | 2006-03-24 | 2009-07-01 | 中国科学院化学研究所 | Preparation method of iron containing polysilazane |
Also Published As
Publication number | Publication date |
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DE3572165D1 (en) | 1989-09-14 |
EP0175384B1 (en) | 1989-08-09 |
JPH0449483B2 (en) | 1992-08-11 |
EP0175384A3 (en) | 1987-07-01 |
CA1242461A (en) | 1988-09-27 |
JPS6177611A (en) | 1986-04-21 |
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